EP0244167B1 - Procédé de préparation de polyaryléthers et polyaryléthercétones - Google Patents

Procédé de préparation de polyaryléthers et polyaryléthercétones Download PDF

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EP0244167B1
EP0244167B1 EP87303619A EP87303619A EP0244167B1 EP 0244167 B1 EP0244167 B1 EP 0244167B1 EP 87303619 A EP87303619 A EP 87303619A EP 87303619 A EP87303619 A EP 87303619A EP 0244167 B1 EP0244167 B1 EP 0244167B1
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salt
process according
naphthalene
acids
sodium
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EP0244167A1 (fr
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Paul Anthony Winslow
Donald Ross Kelsey
Markus Matzner
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BP Corp North America Inc
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BP Corp North America Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols

Definitions

  • a novel process for the preparation of poly(aryl ethers) and poly(aryl ether ketones) comprises reacting an activated dihalobenzenoid compound with a diphenol and/or self-condensing a halophenol whose halogen atom is activated towards nucleophilic substitution reactions.
  • the polymerizations are performed at high temperatures, in an aprotic solvent, and in the presence of a base.
  • the base comprises sodium or an alkaline earth metal carbonate or bicarbonate and a potassium, rubidium or cesium salt of an organic acid.
  • the base comprises sodium or an alkaline earth metal carbonate or bicarbonate and a lithium, sodium or alkaline earth metal salt of an organic acid, optionally in combination with a catalytic amount of a potassium, cesium or rubidium salt catalyst.
  • all of the above reactions may be advantageously performed in the presence of small amounts of cupric or cuprous ions.
  • the process yields high molecular weight, linear, poly(aryl ethers) and poly(aryl ether ketones) possessing excellent thermal stability and physical properties. It is remarkable that the reactions proceed at rates that are significantly higher than those of the prior art processes. Moreover, the polymers obtained are substantially free of undesirable gel particles.
  • PAE poly(aryl ethers)
  • PAEK's are well known; they can be synthesized from a variety of starting materials; and they can be made with different melting temperatures and molecular weights. Most of the PAEK's are crystalline and at sufficiently high molecular weights, they are tough, i.e., they exhibit high values, 4.137 J/cm 3 (>50 ft-lbs/in 3 ) in the tensile impact test (ASTM D-1822). They have potential for a wide variety of uses, and their favorable properties class them with the best of the engineering polymers.
  • PAEK's may be produced by the Friedel-Crafts catalyzed reaction of aromatic diacylhalides with unsubstituted aromatic compounds such as diphenyl ether as described in, for example, U.S. Patent No. 3,065,205. These processes are generally inexpensive processes, however, the polymers produced by these processes tend to be brittle and thermally unstable. In contrast, PAEK's made by nucleophilic aromatic substitution reactions are tough crystalline polymers. Nucleophilic aromatic substitution reactions for producing PAEK's are described in the following references:
  • Example 17 when the reaction is carried out using only sodium carbonate, a polymer is obtained having a reduced viscosity of 0.60 dl/g as measured in concentrated sulfuric acid at 25°C at a concentration of one gm/100 ml.
  • the polymerization was carried out using potassium carbonate instead of sodium carbonate and a high molecular weight polymer was produced (reduced viscosity of 1.55 as measured in concentrated sulfuric acid at 25°C at a concentration of one gm/100 ml.).
  • Example 19 of the patent a mixture of potassium carbonate and sodium carbonate was used.
  • the patent stated that the polymer produced has a high reduced viscosity and a tough off-white film was formed from it. Also, no gel was present in the polymer and the reaction vessel had not become discolored.
  • This invention is directed to a process for making high molecular weight poly(aryl ethers) and poly(aryl ether ketones) in comparatively shorter reaction times overall than by using a combination of sodium carbonate or bicarbonate and a second higher alkali metal carbonate or bicarbonate, or by using a mixture of sodium carbonate or bicarbonate and a potassium, rubidium, or cesium fluoride or chloride or combinations thereof, or by using a lithium and/or alkaline earth metal carbonate and a sodium, potassium, rubidium and/or cesium carbonate.
  • the invention is directed to an improved process for preparing poly(aryl ethers) and poly(aryl ether ketones) by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound, and/or a halophenol, in which the improvement comprises providing to the reaction medium, a combination of sodium or an alkaline earth metal carbonate and/or bicarbonate and a potassium, rubidium, or cesium salt of an organic acid or combinations of various organic salts thereof.
  • the three metals, i.e. potassium, rubidium or cesium are often referred to as higher alkali metals.
  • the invention is directed to an improved process for preparing poly(aryl ethers) and poly(aryl ether ketones) by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound, and/or a halophenol, in which the improvement comprises providing to the reaction medium a combination of sodium or an alkaline earth metal carbonate and/or bicarbonate and a lithium, sodium, or alkaline earth metal salt of an organic acid.
  • this latter reaction can be catalyzed by the addition of a catalytic amount of a potassium, cesium, or rubidium salt catalyst.
  • the process either does not make use at all of any added higher alkali metal compound (or compounds), contrary to the teaching in the prior art; or the process utilizes only catalytic amounts of higher alkali metal compounds which are substantially more effective than when used in prior art processes.
  • all of the above variants may be advantageously performed in the presence of a small amount of cupric or cuprous ions.
  • the process of this invention yields high molecular weight, linear, poly(aryl ethers) and poly(aryl ether ketones) possessing excellent thermal stability and physical properties. It is remarkable that the reactions proceed at rates that are significantly higher than those of the prior art processes. It is even more remarkable that these high reaction rates can be achieved in the presence of catalytic amounts of higher alkali metal salts. Furthermore, it is remarkable that high molecular weight polymers can be prepared even in the absence of added higher alkali metal salts. Moreover, the polymers obtained are relatively free of undesirable gel particles.
  • the poly(aryl ether) polymers suitable for the purposes of this invention are linear thermoplastic polyarylene polyethers containing recurring units of the formula: -0-E-O-E'- wherein E is the residuum of a dihydric phenol, and E' is the residuum of a benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and para to the valence bonds; both of said residua are valently bonded to the ether oxygens through aromatic carbon atoms.
  • aromatic polyethers are included within the class of polyarylene polyether resins described in, for example, U.S. Patents 3,264,536 and 4,175,175.
  • the dihydric phenol be a weakly acidic dinuclear phenol such as, for example, the dihydroxy diphenyl alkanes or the nuclear halogenated derivatives thereof, such as for example, the 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-2-phenyl ethane, bis(4-hydroxyphenyl)methane, or their chlorinated derivatives containing one or two chlorines on each aromatic ring.
  • Other materials also termed appropriately bisphenols are also highly valuable and preferred. These materials are the bisphenols of a symmetrical or unsymmetrical joining group, as for example, ether oxygen (-0-), or hydrocarbon residue in which the two phenolic nuclei are joined to the same or different carbon atoms of the residue.
  • Such dinuclear phenols can be characterized as having the structure: wherein Ar is an aromatic group and preferably is a phenylene group, R and R' can be the same or different inert substituent groups such as alkyl groups having from 1 to 4 carbon atoms, aryl, halogen atoms, i.e., fluorine, chlorine, bromine or iodine, or akoxyl radicals having from 1 to 4 carbon atoms, the d's are independently integers having a value of from 0 to 4, inclusive, and R 1 is representative of a bond between aromatic carbon atoms as in dihydroxyl-diphenyl, or is a divalent radical, including for example, radicals such as -O-, -S-, -S-S- -SO-, -S0 2 , and divalent hydrocarbon radicals such as alkylene, alkylidene, cycloalkylene, cycloalkylidene, or the halogen, alkyl,
  • dihydric polynuclear phenols examples include among others:
  • the E term is defined as being the "residuum of the dihydric phenol" of course refers to the residue of the dihydric phenol after the removal of the two aromatic hydroxyl groups.
  • these polyarylene polyethers contain recurring groups of the residuum of the dihydric phenol and the residuum of the benzenoid compound bonded through aromatic ether oxygen atoms.
  • any dihalobenzenoid or dinitrobenzenoid compound or mixtures thereof can be employed in this invention which compound or compounds has the two halogens or nitro-groups bonded to benzene rings having an electron withdrawing group in at least one of the positions ortho or para to the halogen or nitro group.
  • the dihalobenzenoid or dinitrobenzenoid compound can be either mononuclear, where the halogens or nitro groups are attached to the same benzenoid ring; or polynuclear where they are attached to different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of that benzenoid nucleus.
  • Fluorine and chlorine substituted benzenoid reactants are preferred; the fluorine compounds for fast reactivity and the chlorine compounds for their inexpensive- ness. Fluorine substituted benzenoid compounds are most preferred, particularly when there is a trace of water present in the polymerization reaction system. However, this water content should be maintained below about one percent and preferably below 0.5 percent for best results.
  • An electron withdrawing group is employed as the activator group in these compounds. It should be, of course, inert under the reaction conditions, but otherwise its structure is not critical. Preferred are the strongly activating groups such as the sulfone group bonding two halogen or nitro substituted benzenoid nuclei, as in 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, although such other strong withdrawing groups hereinafter mentioned can also be used with equal ease.
  • the ring contain no electron supplying groups on the same benzenoid nucleus as the halogen or nitro group; however, the presence of other groups on the nucleus or in the residuum of the compound can be tolerated.
  • the activating groups can be basically either ot two types:
  • the polymers may be made with mixtures of two or more dihalobenzenoid or dinitrobenzenoid compounds.
  • the E' residuum of the benzenoid compounds in the polymer structure may be the same of different.
  • the E' term defined as being the "residuum of the benzenoid compound” refers to the aromatic or benzenoid residue of the compound after the removal of the halogen atom or nitro group on the benzenoid nucleus.
  • Preferred polyarylene polyethers prepared according to this invention are those prepared using the dihydric polynuclear phenols of the formulae (1 )-(5) including the derivatives thereof which are substituted with inert substituent groups; in which the R 2 groups represent independently hydrogen, lower alkyl, aryl and the halogen substituted groups thereof, which can be the same or different; and substituted derivatives thereof.
  • the -E- residuum in the polymer structure can actually be the same or different aromatic residua.
  • the preferred dihalobenzenoid compounds are (6), (7), (8), and (9); they may carry inert substituent groups.
  • the most preferred poly(aryl ether) polymers have the repeating units (10), (11), (12), and (13).
  • the poly(aryl ether ketones) prepared according to this invention are characterized as including oligomers, polymers, and copolymers containing repeating units of ether oxygen and keto(carbonyl) interconnected by aromatic diradicals, such as 1,4-phenylene. They may be characterized more specifically by one or more of the following formulae: wherein Ar 1 is independently a divalent aromatic radical selected from phenylene, biphenylene, or naphthylene, X' is independently O, S0 2 , or a direct bond, and a is an integer of from 1 to 4; b, c, d and e are 0 to 1 and preferably d is 0 when b is 1.
  • Preferred poly(aryl ether ketones) include those having repeating units of the formula:
  • the preferred poly(aryl ether ketones) may form copolymers with the following:
  • the process is conducted by reacting a mixture (substantially equimolar amounts when maximum molecular weight is sought) of at least one bisphenol and at least one dihalobenzenoid compound and/or a halophenol.
  • the poly(aryl ethers) are prepared by condensing the bisphenols and dihalo- or dinitrobenzenoid compounds listed above.
  • Halophenols (vide infra) may also be used.
  • the bisphenols useful for the preparation of the poly(aryl ether ketones) may be depicted as follows: wherein the X's can be independently O, S0 2 , or a direct bond and the Ar 2 's can be independently a divalent radical selected from phenylene, biphenylene or naphthylene, most preferably 1,4-phenylene.
  • dihalobenzenoid compounds useful for the preparation of poly(aryl ether ketones) may be depicted as follows: wherein Y is halogen, preferably fluorine or chlorine, the Y's may be the same or different and are ortho or para to the X'; Ar 2 and X' are as defined above with the proviso that the X's ortho or para to the Y's are electron withdrawing groups, i.e., or S0 2 .
  • each aromatic radical is para substituted and most preferably, 1,4-phenylene.
  • the useful halophenols may be depicted as follows: wherein Y, X', and Ar 2 are as defined above with the proviso that the X's ortho or para to Y are electron-withdrawing groups, i.e., or S0 2 .
  • Preferred bisphenols include:
  • the polymerizations are performed in the presence of a base which is composed of sodium or alkaline earth metal carbonate or bicarbonate and of a potassium, rubidium, or cesium salt of an organic acid. Salts of any organic acid are useful.
  • potassium, rubidium, or cesium salts of aliphatic linear or branched acids such as formic, acetic, propionic, butyric, isobutyric, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, 2-methyl-butyric, 3,4-dimethyl-pentanoic, 4,4-dimethyl hexanoic, 2-ethyl-heptanoic, 3-propyl-5,6-dimethyl nonanoic and other similar acids.
  • aliphatic linear or branched acids such as formic, acetic, propionic, butyric, isobutyric, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, 2-methyl-butyric, 3,4-dimethyl-pentanoic, 4,4-dimethyl hexanoic,
  • halo-substituted aliphatic acids such as monochloro-, dichloro-, and trichloroacetic, 2-chloropropionic, 3,5-dichloroheptanoic, bromoacetic, 3-fluorobutyric, and 3,3,3-trichloropropionic acids.
  • Mixed salts such as for example mixtures of potassium and rubidium acetates or mixtures of potassium acetate and potassium benzene sulfonate and the like can also be used.
  • the preferred salts are potassium formate, acetate, propionate, oxalate, benzoate, benzene sulfonate and p-toluene sulfonate.
  • the sodium or alkaline earth metal carbonate or bicarbonate and the potassium, rubidium, or cesium organic salt are used such that the ratio of the higher alkali metal to sodium or alkaline earth metal therein is from about 0.001 to about 0.5, preferably from about 0.001 to about 0.20, and most preferably from 0.01 to about 0.1. In another preferred embodiment, from 0.001 to about 0.5 atoms of alkali metal (derived from the alkali metal organic salt) is used for each phenol group.
  • alkali metal derived from the alkali metal organic salt
  • cesium is a more active metal and potassium is a less active metal, so that less cesium and more potassium are used.
  • the ratio of carbonate and bicarbonate anions to the phenolic groups be about 0.5 to 1.0, respectively. However, higher and lower ratios are also possible.
  • this invention is directed to an improved process for preparing poly(aryl ethers) and poly(aryl ether ketones) by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound, and/or a halophenol in the presence of a combination of sodium or alkaline earth metal carbonate or bicarbonate and a lithium, sodium, or alkaline earth metal salt of an organic acid and substantially in the absence of higher alkali metal salts.
  • the salts of organic acids that are useful are the same as those listed above.
  • Preferred salts are the formates, acetates, propanoates, benzoates, benzene sulfonates and p-toluene sulfonates. Sodium salts are most preferred.
  • the polycondensation is preferably conducted in the presence of an essentially stoichiometric amount of sodium or alkaline earth metal carbonate or sodium or alkaline earth metal bicarbonate, i.e., the ratio of carbonate and bicarbonate anions to the phenolic groups should be about 0.5 and 1.0, respectively.
  • an essentially stoichiometric amount of sodium or alkaline earth metal carbonate or sodium or alkaline earth metal bicarbonate i.e., the ratio of carbonate and bicarbonate anions to the phenolic groups should be about 0.5 and 1.0, respectively.
  • the amount of the lithium, sodium, or alkaline earth metal salt is in the range of from about 0.01 to about 0.5 moles per mole equivalent of sodium or alkaline earth metal carbonate or bicarbonate; and preferably from about 0.02 to about 0.3 moles per mole equivalent.
  • the amount of the lithium, sodium, or alkaline earth metal salt can be adjusted to obtain the desired reaction rate and, hence, these salts may be used
  • This latter polymerization can be catalyzed by the addition of a catalytic amount of a potassium, cesium or rubidium salt.
  • the polycondensation of a bisphenol with a dihaloaromatic monomer is, once again, conducted in the presence of an essentially stoichiometric amount of sodium or alkaline earth metal carbonate or bicarbonate, although a deficiency or an excess of carbonate or bicarbonate can be used.
  • the amount of the lithium, sodium, or alkaline earth metal salt is from about 0.005 to about 0.5 moles per mole equivalent of sodium or alkaline earth metal carbonate or bicarbonate; and preferably from about 0.01 to about 0.2 moles per mole equivalent.
  • the amount of the higher alkali metal salt catalyst is from about 0.00001 to about 0.05 gram-atom of the higher alkali metal per mole equivalent of sodium or alkaline earth metal carbonate or bicarbonate; and such that the ratio of gram-atoms of the higher alkali metal to the mole equivalent of the lithium, sodium, or alkaline earth metal salt is less than one.
  • the preferred amount of the lithium, sodium, or alkaline earth metal salt it is preferred to employ from about 0.00002 to about 0.01 gram-atoms of the higher alkali metal per mole equivalent of sodium or alkaline earth metal carbonate or bicarbonate.
  • the gram-atom ratio of the higher alkali metal to the combined total gram equivalents of lithium, sodium and alkaline earth metal, (carbonate, bicarbonate, and organic salt) should be less than about 0.05, preferably less than about 0.005, and most preferably less than about 0.001.
  • the amount of the lithium, sodium or alkaline earth metal salt and the amount of the higher alkali metal salt catalyst can be adjusted separately or simultaneously to obtain the desired reaction rate and, hence, these salts may be used in amounts greater or lesser than the ranges stated above.
  • the lithium, sodium, or alkaline earth metal salts of organic acids that are useful are the same as those listed above.
  • Preferred salts are the formates, acetates, propanoates, benzoates, benzene sulfonates and p-toluene sulfonates.
  • Sodium salts are most preferred.
  • the higher alkali metal salt catalysts are of the general formula MX" where M is potassium, cesium or rubidium; X" is the residue of an organic acid (vide supra); the residue of an inorganic acid such as carbonate, bicarbonate, halide and the like; the residue of a phenol such as phenoxide, naphthoxide, halo- and/or alkyl-substituted phenoxides, naphthoxides and the like; the residue of an alcohol such as methoxide, ethoxide, propoxide, n-butoxide, t-butoxide and the like; and a hydroxyl group.
  • MX is the residue of an organic acid (vide supra); the residue of an inorganic acid such as carbonate, bicarbonate, halide and the like; the residue of a phenol such as phenoxide, naphthoxide, halo- and/or alkyl-substituted phenoxides, naphthoxide
  • salts wherein X" is an acetate, propanoate, oxalate, trichloroacetate, benzoate, benzene sulfonate, p-toluene sulfonate, trifluoromethane sulfonate, methane sulfonate, carbonate, bicarbonate, fluoride, chloride, and phenoxide are preferred. Potassium salts are the most preferred.
  • cupric or cuprous ions A wide range of copper compounds may be used, both cupric and cuprous compounds being usable in accordance with the present invention.
  • the copper compounds used should be stable under the polymerization conditions and it is preferred that the copper compounds be essentially anhydrous. Copper compounds which can be used include cuprous chloride, cupric chloride, cupric acetylacetonate, cuprous acetate, cupric hydroxide, cuprous oxide, cupric oxide, basic cupric carbonate and basic cupric chloride. Although a basic copper compound may be used, it is still necessary to use an at least stoichiometric amount of the sodium or alkaline earth metal carbonate or bicarbonate.
  • the proportion of the copper compound used is preferably not more than one mole percent based on the total reagents employed; preferably, less than 0.4 mole percent of the copper compound based on the reagents is used. It is generally desirable to employ at least 0.1 mole percent of the copper derivative. Obviously, the optimum amount of the cupric or cuprous ions will depend on the reagents and on the type of the copper derivative employed.
  • the total amount of sodium or alkaline earth metal carbonate and/or bicarbonate and of the alkali and alkaline earth metal salt should be such that there is at least one atom or atom equivalent of total alkali and alkaline earth metal for each phenol group, regardless of the anion (carbonate, bicarbonate, carboxylate, etc).
  • a halophenol there should be at least one atom or atom equivalent of alkali and alkaline earth metal per mole of halophenol.
  • from about 1 to about 1.2 atoms of sodium for each phenol group are used.
  • An excess of total alkali and alkaline earth metal may be employed.
  • alkali and alkaline earth metal there may be about 1 to about 1.7 atoms or atom equivalents of alkali and alkaline earth metal per phenol group. While the use of a large excess of alkali and alkaline earth metal may give rise to faster reactions, there is the attendant risk of cleavage of the resulting polymer, particularly when using high temperatures and/or the more active alkali metal salts.
  • the reaction is carried out by heating a mixture of one or more bisphenols and one or more dihalobenzenoid compounds and/or halophenols at a temperature of from about 100 ° to about 400 ° C.
  • the reaction is conducted in the presence of added base as hereinabove defined.
  • the sodium or alkaline earth metal carbonate or bicarbonate and the organic salts should be anhydrous although, if hydrated salts are employed where the reaction temperature is relatively low, e.g., 100 ° to 250 ° C., the water should be removed, e.g., by heating under reduced pressure, prior to reaching the reaction temperature. It is also preferred that the higher alkali metal salt catalysts be anhydrous; however, these latter salts are employed in amounts such that the hydrated forms can also be used.
  • reaction temperatures >250 ° C
  • an entraining organic medium such as toluene, xylene, chlorobenzene, and the like can be used to remove the water from the reaction mixture.
  • a bisphenol and dihalobenzenoid compound are employed, they should be used in substantially equimolar amounts when maximum molecular weight is sought. However, a slight excess, up to 5 mole percent of the dihalide or of the diphenol, may be employed, if desired. An excess of one over the other leads to the production of low molecular weight products which can be desirable when the process is directed to making lower molecular weight PAEK, for example, for block polymer formation.
  • the reaction may be carried out in the presence of an inert solvent, or partially in the absence of a solvent, or in the absence of a solvent.
  • a solvent is employed and is an aliphatic or aromatic sulphoxide or sulphone of the formula R-S(O)x-R' where x is 1 or 2 and R and R' are alkyl or aryl groups and may be the same or different. R and R' may together form a divalent radical.
  • Preferred solvents include dimethyl sulphoxide, dimethyl sulphone, sulpholane (1,1 dioxothiolan), or aromatic sulphones of the formula where R 2 is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and R 3 and R' ⁇ , which may be the same or different, are hydrogen atoms or phenyl groups.
  • aromatic sulphones examples include diphenylsulphone, ditolyl sulphone, tolylphenyl sulphone, dibenzothiophene dioxide, phenoxathiin dioxide and 4-phenylsulphonyl biphenyl.
  • Diphenylsulphone is the prefered aromatic sulfone solvent.
  • Other very useful and preferred solvents that may be used, include N,N-dimethyl formamide, N-methyl-2-pyrolidone, N,N-dimethylacetamide, and N-cyclohexyl pyrolidone.
  • the reaction is started in a relatively low boiling polar aprotic solvent such as dimethyl formamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrolidone, and the like. Heating at reflux results in the formation of low molecular weight product with attendant precipitation.
  • the solvent may be removed and the low molecular weight product may be advanced if desired, by solid-state polymerization, i.e., by heating to a temperature in the range of from about 200 ° to about 400 ° C; preferably, an inert atmosphere is maintained during this latter step.
  • the reaction temperature is in the range of from about 100 ° to about 400 ° C and will depend on the nature of the reactants and the solvent, if any, employed.
  • the preferred temperature is above about 130 ° C for the preparation of poly(aryl ethers) and above about 250 ° C for the preparation of the highly crystalline poly(aryl ether ketones).
  • the reactions are preferably carried out at ambient pressure. However, higher or lower pressure can also be used.
  • the reaction is generally carried out in an inert atmosphere.
  • poly(aryl ether ketones) For the production of some poly(aryl ether ketones), it may be desirable to commence reaction at one temperature, e.g., between 200 ° and 250 ° C and to increase the temperature as reaction ensues. This is particularly necessary when making high molecular weight polymers having only a low solubility in the solvent. Thus, there it is desirable to increase the temperature progressively to maintain the polymer in solution as its molecular weight increases.
  • the use of the organic salts as part of the base results in increased rates of polymerization.
  • the observed increase in the rate can be as high as an order of magnitude, and even higher, when compared to rates that are obtained with the previously know systems.
  • the use of the organic ss.'s also allows the preparation of polymers with useful molecular weights even in the absence of higher alkali metal compounds or, optionally, in the presence of catalytic amounts of higher alkali metal salts. These useful high molecular weights are unattainable using the previously known systems.
  • the poly(aryl ethers) and poly(aryl ether ketones) exhibit a reduced viscosity of from about 0.05 to about 5.0, and preferably, from about 0.1 to about 2.0 dl/g as measured in an appropriate solvent at 25°C.
  • the poly(aryl ethers) and poly(aryl ether ketones) prepared according to this invention may include mineral fillers such as carbonates including chalk, calcite and dolomite; silicates including mica, talc, wol- lastonite; silicon dioxide; glass spheres; glass powders; aluminum; clay; quartz; and the like. Also, reinforcing fibers such as fiberglass, carbon fibers, and the like may be used.
  • the polymers may also include additives such as titanium dioxide; thermal stabilizers, ultraviolet light stabilizers, plasticizers, and the like.
  • poly(aryl ethers) and poly(aryl ether ketones) of this invention may be fabricated into any desired shape, i.e., moldings, coatings, films, or fibers. They are particularly desirable for use as electrical insulation for electrical conductors.
  • a poly(aryl ether ketone) of the following structure was prepared in the following manner.
  • a 250 ml flask was equipped with a mechanical stainless steel stirrer, nitrogen sparge tube, thermocouple, Dean Stark trap and condenser. The apparatus was charged with
  • the apparatus was evacuated and filled with nitrogen by means of a Firestone valve connected to the top of the condenser. A flow of nitrogen was begun as 35 ml of xylene were added and the contents of the flask carefully heated by means of a heating mantle and temperature controller to melt the diphenyl sulfone. The reaction mixture was stirred and heated to 200 ° C and held for one hour, then held at 250°C for 15 minutes, and finally at 320 ° C for 1.5 hours. The viscous reaction mixture was poured from the reaction flask, allowed to solidify, and ground to a fine powder.
  • the product was refluxed in acetone (700 ml), followed by 5 percent of aqueous hydrochloric acid solution (700 ml); and washed with water (two times using 500 ml of water each time) and acetone (two times using 500 ml each time).
  • the final product was dried in a vacuum oven at 100 ° C for approximately 24 hours.
  • the product had a reduced viscosity of 1.19 dl/g (in concentrated sulfuric acid at 1 g/100 ml at 25°C).
  • Example 1 was repeated with the reaction time shortened to 10 minutes at 320 ° C. The results are listed in Table I.
  • Example 2 was repeated with the reaction time shortened to 7 minutes at 320 ° C. The results are listed in Table I.
  • the reduced viscosity of the polymer measured on a solution of one gram of polymer in 100 ml concentrated sulfuric acid at 25 ° C was 0.60 dl/g. This value indicates that a relatively low molecular weight polymer was obtained.
  • the polymerization was performed in a manner similar to that of Control C with potassium acetate in place of potassium fluoride.
  • the polymer was isolated as given in previous examples, except using 5 percent HCI in place of the oxalic acid extraction.
  • the reduced viscosity (one percent in concentrated sulfuric acid, at 25°C) of the polymer was 3.97 dl/g.
  • the polymer solution in sulfuric acid showed no evidence of gel particles for this very high molecular weight polymer.
  • Control B The procedure of Control B was repeated using only sodium carbonate (0.2346 moles). After 120 minutes at 320 ° C and end-capping with BFBB, a polymer having a reduced viscosity (one gram/100 ml concentrated H 2 S0 4 at 25°C) of 0.44 dl/g was obtained.
  • the polymerization was conducted as in Example 7 except with sodium benzoate (0.023 moles, 3.31 g) in place of sodium acetate. Upon reaching the final reaction temperature at 320 ° C, the reaction mixture was creamy white. After 32 minutes at 320 ° C, the polymer was end-capped with BFBB. The final polymer reduced viscosity was 1.25 dl/g (one gram/100 ml concentrated H 2 S0 4 at 25 ° C).
  • the polymerization was repeated as in Example 10 but with less sodium benzoate (0.0115 moles,1.66 g). After 30 minutes at 320 ° C, a polymer sample was taken, and after a total of 37 minutes at 320 ° C, the polymer was end-capped with BFBB. The reduced viscosities were 1.19 dl/g and 1.33 dl/g for the polymer sample and the final polymer, respectively (one gram/100 ml concentrated H 2 S0 4 at 25 ° C).
  • Example 11 The polymerization of Example 11 was repeated except that even less sodium benzoate (0.0046 moles, 0.66 g) was used. A polymer sample taken after 35 minutes at 320°C had a reduced viscosity of 1.54 dl/g. The final polymer sample obtained after end-capping with BFBB had a reduced viscosity of 1.39 dl/g (one gram/100 ml concentrated H 2 S0 4 at 25°C).
  • the reduced viscosity measured on a solution of 1 g polymer in 100 ml concentrated sulfuric acid, at 25 ° C was 2.06 dl/g.
  • the polymerization was conducted essentially as in Example 13 except that the amount of sodium acetate was reduced to 0.98 g (0.012 moles). After 12 minutes at 320 ° C, 1,4-bis(4-fluorobenzoyl)-benzene [BFBB](1.48 g, 0.0046 moles) along with 35 g diphenyl sulfone were added to the very viscous reaction mixture to end-cap the polymer. The reaction mixture was quenched 10 minutes later and worked up as in Example 13. The reduced viscosity was 2.21 dl/g.
  • Example 14 The polymerization of Example 14 was conducted with potassium carbonate (0.0006 moles, 0.083 g) in place of potassium fluoride. After 12 minutes at 320°C, a reaction sample was taken and after an additional two minutes, the reaction mixture was poured out and cooled. The polymer sample reduced viscosity was 1.45 dl/g and the final polymer reduced viscosity was 1.66 dl/g. The K/Na ratio in this example was 0.0025, essentially the same as in Example 14.
  • the polymerization was conducted essentially as in Example 13 except that the amount of potassium fluoride was reduced to 0.0138 g (0.000237 moles). After 30 minutes at 320 ° C LiCI (0.10 g, 0.0023 moles) and 5 g diphenyl sulfone were added; after 6 minutes BFBB and 11 g diphenyl sulfone were added as in Example 14 and the reaction temperature was reduced to 300 ° C. The reaction mixture was quenched after 20 minutes. The results are listed in Table III.
  • the polymer was compression molded at 400 ° C to give a tough film with the following properties:
  • the polymer exhibited a melt flow (400 ° C, 10P) of 1.5 dg/min. Its melt stability at 400 ° C was excellent.
  • the polymerization was conducted essentially as in Example 16 except that the amount of sodium acetate was reduced to 0.94 g (0.115 moles).
  • a reaction sample was taken after 15 minutes at 320°C; after 25 minutes LiCI (0.042 g, 0.001 moles and 5 g diphenyl sulfone were added and the reaction temperature reduced to 300 ° C and a second reaction sample was taken.
  • the rection was quenched 25 minutes after the BFBB was added and worked up as in Example 13. The results are shown in Table III.
  • Example 17 The polymerization was conducted essentially as in Example 17 except that a slightly lower amount of potassium fluoride was charged and except that the polymer was not end-capped. A reaction sample was taken after 15 minutes at 320 ° C; after 30 minutes the viscous reaction mixture was quenched by pouring it into a pan. The polymer was isolated as in Example 13 and the results are shown in Table III.
  • the polymerization was conducted in a manner similar to that of Example 17, except with sodium benzoate (0.0046 moles, 0.66 g) in place of sodium acetate. After 15 minutes at 320 ° C, a reaction sample was taken, the polymer was end-capped using lithium chloride and BFBB, and quenched 15 minutes later. The reduced viscosity of the polymer sample was 1.29 dl/g and of the final isolated polymer 1.35 dl/g. (1 g/100 ml. concentrated HpSO 4 at 25 ° C). The K/Na ratio in this example was 0:00050.
  • Example 17 The polymerization of Example 17 was repeated with about half the potassium fluoride (0.000118 moles, 0.0069 g) and the polymer was not end-capped. After 33 minutes at 320 ° C, the reaction mixture was quenched by pouring it out. The final polymer reduced viscosity was 2.43 dl/g (1 g/100 ml concentrated H 2 S0 4 at 25 ° C). The K/Na ratio in this example was 0.000245, about half that in Example 17; and yet the molecular weight was even higher than that obtained in Examples 17 and 18.
  • reaction mixture was purged with an inert atmosphere and heated as follows:

Claims (31)

1. Procédé pour préparer des poly (éthers aryliques) et des poly(éther-cétones aryliques) par réaction d'un mélange d'au moins un bisphénoi et d'au moins un composé dihalogénobenzénoïde et/ou d'un halogénophénol, dont le perfectionnement comprend l'apport à la réaction d'une base qui est une combinaison d'un carbonate et/ou bicarbonate de sodium ou d'un métal alcalino-terreux et d'un sel de potassium, rubidium ou césium d'un acide organique ou de combinaisons de tels sels organiques.
2. Le procédé de la revendication 1, dans lequel le rapport des atomes-grammes totaux de potassium, de rubidium ou de césium aux équivalents-grammes totaux de sodium ou du métal alcalino-terreux est de 0,001 à 0,5.
3. Un procédé perfectionné pour préparer des poly(éthers aryliques et des poly (éther-cètones aryliques) par réaction d'un mélange d'au moins un bisphenol et d'au moins un composé dihalogénobenzénoïde et/ou d'un halogénophénol, dont le perfectionnement comprend l'apport à la réaction d'une base qui est une combinaison d'un carbonate ou bicarbonate de métal alcalino-terreux et d'un sel de lithium, de sodium ou de métal alcalino-terreux d'un acide organique ou de combinaisons de tels sels organiques.
4. Un procédé selon la revendication 3, dans lequel la base est une combinaison de carbonate ou de bicarbonate de sodium et d'un sel de sodium d'un acide organique ou une combinaison de tels sels organiques.
5. Le procédé de la revendication 3 ou 4, dans lequel la quantité de sel (organique) de lithium, de sodium ou de métal alcalino-terreux est de 0,01 à 0,05 mole par équivalent molaire de carbonate ou bicarbonate de sodium ou de métal alcalino-terreux.
6. Le procédé selon la revendication 3 ou 4 qui est catalysé par l'addition d'un quantité catalytique de sel de potassium, de césium ou de rubidium.
7. Le procédé selon la revendication 6, dans lequel la quantité du sel (organique) de lithium, de sodium ou de métal alcalino-terreux est de 0,005 à 0,5 mole par équivalent molaire de carbonate ou bicarbonate de sodium ou de métal alcalino-terreux.
8. Le procédé de la revendication 6, dans lequel la quantité du catalyseur constitué de sel de potassium, de rubidium ou de césium est dans la gamme de 0,00001 à 0,05 atome-gramme par équivalent molaire de carbonate ou bicarbonate de sodium ou de métal alcalino-terreux.
9. Le procédé de la revendication 6, dans lequel le rapport des atomes-grammes du catalyseur constitué de sel de potassium, de rubidium ou de césium aux équivalents molaires de sel (organique) de lithium, de sodium ou de métal alcalino-terreux est inférieur à un.
10. Le procédé de la revendication 6, dans lequel le rapport des atomes-grammes du catalyseur constitué de sel de sodium, de rubidium ou de césium aux équivalents-grammes totaux combinés de lithium, sodium et métal alcalino-terreux (carbonate, bicarbonate et sel organique) est inférieur à environ 0,05.
11. Le procédé selon les revendications 1, ou 3, ou 4, ou 6, où le rapport des anions carbonate et bicarbonate aux groupes phénoliques est respectivement d'environ 0,5 et 1,0.
12. Un procédé selon les revendications 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide aliphatique linéaire ou rafimié choisi parmi les acides formique, acétique, propioniqué, butyrique, isobutyri- que, pentanoïque, hexanoïque, heptanoïque, octanoïque, nonanoïque, décanoïque, 2-méthylbutyrique, 3,4-diméthylpentanoïque, 4,4-diméthylhexanoïque, 2-éthylheptanoïque et 3-propyl-5,6-diméthylnonanoï- que.
13. Un procédé selon les revendications 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide aliphatique halogéno-substitué choisi parmi les acides monochloro-, dichloro- et trichloroacétique, 2-chloropropionique, 3,5-dichloroheptanoïque, bromoacétique, 3-fluorobutyrique et 3,3,3-trichloropropio- nique.
14. Un procédé selon les revendiactions 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide aromatique mono ou polynucléaire choisi parmi les acides benzoïque, toluique, 3,4-diméthylbenzoïque, 2-chlorobenzoïque, 3,4-dichlorobenzoïque, 2-bromobenzoïque, 2-chloro-4-méthylbenzoïque, 2-fluoro-3- éthylbenzoïque, d'autres acides benzoïques alcoyl- et/ou halogéno-substitués, les acides naphtalènecarboxyliques, les acides naphtalènecarboxyliques alcoyl-substitués, tels que l'acide 3-méthyinaphtaiè- ne-1-carboxylique, l'acide 6-éthylnaphtalène-2-carboxylique, les acides naphtalènecarboxyliques halogénosubstitués, tels que l'acide 4-chloronaphtalène-2-carboxylique, et les acides phénanthrènecar- boxyliques et anthracènecarboxyliques.
15. Un procédé selon les revendications 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide arylaliphatique choisi parmi les acides phénylacétique, diphénylacétique, 1-naphtylacétique, 2-naphtylacétique, 4-chlorophénylacétique, 4-méthylphenylacétique, 3-bromo-1-naphtylacétique, 4-chloro-2-naphthylacétique, 3-(6-chloro-1-naphtyl) propionique, 3-(4-éthylphényl) butyrique, 3-méthyl-4-(2-éthyl-4-chlorophényl) butyrique, 3-phénylhexanoïque et 7-phénylnonanoïque.
16. Un procédé selon les revendications 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide carboxylique hétérocylique choisi parmi les acides furanne-2-carboxylique, furanne-3-carboxylique, thiophène-2-carboxylique, thiophène-3-carboxylique et les acides pyridine-, quinoléine- et isoquinoléine- carboxyliques; les acides hétérocycliques alcoyl-, aryl- et halogéno-substitués choisis parmi acides 2-méthyl-furanne-3-carboxylique, 4-chloropyridine-2-carboxylique, 2-méthyl-4-oxazolecarboxylique et 2-propylpyrazine-3-carboxylique.
17. Un procédé selon les revendications 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide di- carboxylique choisi parmi les acides oxalique, malonique, succinique, adipique, subérique, azélaique, a-bromoglutarique, p,pl-diméthylglutarique, a,a'-dichlorosubérique, maléique, fumarique, phtalique, isophtalique, téréphtalique, - naphtalène-t,2-dicarboxylique,- naphtalène-2,3-dicarboxylique, naphtalène-1,5- ; -1,6- ; -1,7- ; -1,8- ; -2,4- ; -2,5- et -2,6-dicarboxyliques, pyridine-2,3-dicarboxylique et furanne-2,3-dicarboxylique.
18. Un procédé selon les revendications 1, ou 3, ou 5, ou 6, où le sel organique est un sel d'un acide phosphonique ou phosphinique aliphatique, aromatique ou hétérocyclique choisi parmi les acides métha- nesulfonique, éthanesulfonique, propanesulfonique, benzènesulfonique, 1-naphtalènesulfonique, 2-naphtalènesulfonique, 1-naphtalènesulfinique, 1,8-naphtalènedisulfonique, 2,6-naphtalènedisulfonique, 4-méthylbenzènesulfinique, p-toluènesulfonique, 3,4-dichlorobenzènesulfonique, 6-chloronaphtalène-1-sulfonique, quinoléine-2-sulfonique, 4-pyridine-sulfonique, 2-thiophènesuifonique, 3-thiophènesulfo- nique, 3-méthyl-2-furannesulfinique et 3-propyl-2-furannesulfonique.
19. Un procédé selon les revendications 1, ou 3, ou 4, ou 6, où le sel organique est un sel d'un acide phosphonique ou phosphinique aliphatique, aromatique ou hétérocyclique choisi parmi les acides métha- nephosphonique, éthanephosphonique, benzènephosphinique, benzènephosphonique, 1-naphtalènephosphonique, 2-naphtalènephosphonique, 1-naphtalènephosphinique, 1,8-naphtalènediphosphonique, 2,6-naphtalènediphosphonique, 4-méthylbenzènephosphinique, 4-éthylbenzènephosphonique, 3,4-di- chlorobenzènephosphonique, 3,4-dibromobenzènephosphonique, 3-chloro-4-méthylbenzènephospho- nique, 6-chloro-1-naphtalènephosphonique, 2-quinoléinephosphonique, 2-thiophènephosphonique, 3-thiophènephosphonique, 3-thiophènephosphinique, 3-chloro-2-furanne-phosphinique et 3-propyl-2-fu- rannephosphonique.
20. Le procédé selon la revendication 1, dans lequel le sel organique de potassium, de rubidium ou de césium est un sel de potassium.
21. Le procédé selon les revendications 1 ou 2, où le sel organique est choisi dans le groupe constitué par formiate, acétate, propionate, oxalate, benzoate, benzènesulfonate et p-toluènesulfonate.
22. Le procédé selon les revendiactions 3, ou 4, ou 6, où le sel organique est choisi dans les groupe constituè par formiate, acétate, propionate, benzoate, benzènesulfonate et p-toluènesulfonate.
23. Le procédé selon les revendications 3, ou 6, ou 22, où le sel organique est un sel organique de sodium.
24. Le procédé selon la revendication 6, où le catalyseur constitué d'un sel de potassium, de rubidium ou de césium a pour formule MX"
dans laquelle M est choisi le potassium, le rubidium et le césium.
25. Le procédé selon la revendication 24, dans lequel M est le potassium.
26. Le procédé selon la revendication 24 ou 25, dans lequel X" est choisi parmi les anions des acides organiques et minéraux, les phénolates, les phénolates halogéno- et/ou alcoyl-substitués, les naphtylates, les naphtylates halogéno- et/ou alcoyl-substitués, les alcoolates et hydroxyde.
27. Le procédé selon les revendications 24, ou 25, ou 26, où X" est choisi dans le groupe constitué par acétate, propionate, oxalate, benzoate, benzènesulfonate, p-toluènesulfonate, trichloroacétate, tri- fluorométhanesulfonate, méthanesulfonate, carbonate, bicarbonate, chlorure, phénate, méthylate, éthy- late, propylate, n-butylate et tert-butylate.
28. Le procédé selon les revendications 1, ou 3, ou 4, ou 6, où on utilise un composé cuivrique ou cuivreux en une quantité d'au moins 0,1% molaire relativement à la totalité des composés réagissants phénoliques et halogénobenzénoïdes utilisés.
29. Le procédé selon la revendication 28, où le composé de cuivre est choisi dans le groupe du chlorure cuivreux, du chlorure cuivrique, de l'acétylacétonate cuivrique, de l'acétate cuivreux, de l'hydroxyde cuivrique, de l'oxyde cuivreux, de l'oxyde cuivrique, du carbonate cuivrique basique et du chlorure cuivrique basique.
30. Un procédé perfectionné pour la préparation de poly (éther-cétones aryliques) par réaction d'un mélange d'au moins un bisphénol et d'au moins un composé dihalogénobenzénoïde et/ou d'un halogénophénol, où le perfectionnement comprend l'apport à la réaction d'une base qui est une combinaison de carbonate et/ou bicarbonate de sodium et d'un sel de potassium, de rubidium ou de césium d'un acide organique ou de combinaisons de divers sels organiques de ceux-ci.
31. Un procédé selon la revendication 30, où le sel de l'acide organique est choisi parmi les sels de potassium, de rubidium ou de césium de (a) les acides aliphatiques linéaires ou ramifiés, (b) les acides aliphatiques halogéno-substitués, (c) les acides aromatiques mono ou polynucléaires, (d) les acides arali- phatiques ramifiés ou linéaires, (e) les acides carboxyliques hétérocycliques, (f) les acides dicarboxyli- ques aliphatiques, aromatiques ou hétérocycliques, (g) les acides sulfoniques ou sulfiniques aliphatiques, aromatiques ou hétérocycliques ou (h) les acides phosphoniques ou phosphiniques aliphatiques, aromatiques ou hétérocycliques.
EP87303619A 1986-04-25 1987-04-24 Procédé de préparation de polyaryléthers et polyaryléthercétones Expired - Lifetime EP0244167B1 (fr)

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US06/855,596 US4748227A (en) 1986-04-25 1986-04-25 Process for preparing poly(aryl ether)ketones using a sodium carbonate/organic acid salt catalyst
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US07/037,839 US4774314A (en) 1986-04-25 1987-04-13 Preparing poly(aryl ethers) using alkaline earth metal carbonates, organic acid salts, and optionally copper compounds, as catalysts

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DE68908016T2 (de) * 1988-05-31 1994-03-03 Mitsubishi Chem Ind Verfahren zur Herstellung eines Phenolats und dessen Verwendung in einem Verfahren zur Herstellung eines aromatischen Polyether-Ketons.
DE3926263A1 (de) * 1989-08-09 1991-02-14 Hoechst Ag Verfahren zur herstellung eines aromatischen polyethers
EP0528266A3 (en) * 1991-08-20 1993-05-05 Basf Aktiengesellschaft Method for the production of polyarylethers
US5268444A (en) * 1993-04-02 1993-12-07 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phenylethynyl-terminated poly(arylene ethers)
JP2005146196A (ja) * 2003-11-19 2005-06-09 Sumitomo Chemical Co Ltd 芳香族ポリエーテルの製造方法
DE102004062761A1 (de) 2004-12-21 2006-06-22 Degussa Ag Verwendung von Polyarylenetherketonpulver in einem dreidimensionalen pulverbasierenden werkzeuglosen Herstellverfahren, sowie daraus hergestellte Formteile
TWI461458B (zh) 2007-08-10 2014-11-21 Solvay Advanced Polymers Llc 改良之聚（芳基醚酮）類及製造彼等之方法
DE102008001873A1 (de) 2008-05-20 2009-11-26 Evonik Degussa Gmbh Kerbschlagzähe Polyarylenetherketon-Formmasse
DE102008002460A1 (de) 2008-06-17 2009-12-24 Evonik Degussa Gmbh Verfahren zur Herstellung von Polyarylenetherketonen
DE102009045892A1 (de) 2009-10-21 2011-04-28 Evonik Degussa Gmbh Folie aus Polyarylenetherketon
DE102011007837A1 (de) * 2011-04-21 2012-10-25 Evonik Degussa Gmbh Kleberloser Verbund aus einer Polyarylenetherketon- und einer Metallfolie
WO2019186085A1 (fr) * 2018-03-28 2019-10-03 Victrex Manufacturing Limited Copolymères et leur procédé de fabrication
GB202010909D0 (en) 2020-07-15 2020-08-26 Victrex Mfg Ltd Copolymers, their preparation and use
CN113527661B (zh) * 2021-08-16 2022-07-15 吉林省中研高分子材料股份有限公司 一种聚（芳基醚酮）的制备方法及聚（芳基醚酮）
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